ZnFe2O4 was thermally synthesised through the mediation of different polymers such as Poly(vinyl alcohol), Poly(vinyl pyrrolidone) and Poly(ethylene glycol) to prevent the unwanted agglomeration. The Rietveld refinement of the XRD spectra confirmed the sample to be fcc, while the FESEM/TEM micrographs exhibited the formation of spherical nanoparticles. The TGA/DSC analysis confirmed that the sample is stable up to 500°C. The dielectric, impedance and modulus spectroscopy as a function of temperature up to 200°C and within the frequency range of 20 Hz to 2 MHz confirm a single non-Debye type relaxation behaviour at different temperatures (well fitted by the KWW (Kohlrausch–Williams–Watts) function) attributed to the grain boundary/MWS polarisation present in the samples. The modulus and impedance master curve confirmed the distribution of relaxation times being independent of temperature. The AC conductivity phenomenon is explained using the CBH (correlated barrier hopping) model, satisfying Jonscher's universal power law with exponents in the range of [0,1] with an activation energy in the range of 0.4–0.8 eV. The obtained optical spectra of the samples with the help of UV-visible/PL spectra evaluate the direct energy band gap to be from 1.7 eV to 2.8 eV and these ferrites may be suitable for high-frequency as well as for optoelectronic applications.